EP1655334B1 - Composition de polyéthylène multimodal avec homogénéité améliorée - Google Patents
Composition de polyéthylène multimodal avec homogénéité améliorée Download PDFInfo
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- EP1655334B1 EP1655334B1 EP04026094A EP04026094A EP1655334B1 EP 1655334 B1 EP1655334 B1 EP 1655334B1 EP 04026094 A EP04026094 A EP 04026094A EP 04026094 A EP04026094 A EP 04026094A EP 1655334 B1 EP1655334 B1 EP 1655334B1
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- polyethylene composition
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- base resin
- molecular weight
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- 239000000203 mixture Substances 0.000 title claims description 103
- 239000004698 Polyethylene Substances 0.000 title claims description 55
- -1 polyethylene Polymers 0.000 title claims description 53
- 229920000573 polyethylene Polymers 0.000 title claims description 53
- 239000011347 resin Substances 0.000 claims description 45
- 229920005989 resin Polymers 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 28
- 238000012360 testing method Methods 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 39
- 238000013329 compounding Methods 0.000 description 29
- 241000519995 Stachys sylvatica Species 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 18
- 238000009826 distribution Methods 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- 235000019241 carbon black Nutrition 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 229920006158 high molecular weight polymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007863 gel particle Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 238000010094 polymer processing Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000721701 Lynx Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
Definitions
- the present invention concerns a multimodal polyethylene composition comprising a low molecular weight fraction, a high molecular weight fraction and an ultrahigh molecular weight fraction, with improved homogeneity. Furthermore, the present invention relates to a process for the production of such a composition as well as to the use of such a composition for the production of a pipe, for moulding applications, and wire and cable applications.
- Multimodal polyethylene compositions are frequently used e.g. for the production of pipes due to their favourable physical and chemical properties as e.g. mechanical strength, corrosion resistance and long-term stability.
- the fluids such as water or natural gas
- transported in a pipe often are pressurized and have varying temperatures, usually within a range of 0°C to 50°C, it is obvious that the polyethylene composition used for pipes must meet demanding requirements.
- homogeneity is known to be a critical property, because low degrees of homogeneity adversely affect e.g. the surface properties and other properties of the polymer composition.
- mixing of the different fractions the composition is consisting of must be reached down to the microscopic scale.
- white spots occur in the compounded material. These white spots usually have a size of below 10 to about 50 micrometer and consist of high molecular weight polymer particles that have not been adequately compounded in the composition. Further, when compounding polymer compositions e.g. for the production of films, gel particles with a size of about 0.01 to 1 mm often occur. These gel particles also consist of high molecular weight polymer particles not adequately compounded and appear as disfiguring inhomogeneities in the finished film. Still further, inhomogeneities in multimodal polymer compositions may also cause waviness of the surface of articles produced thereof.
- ISO 18553 As a measure for the homogeneity in multimodal resins the ISO 18553 test can be applied.
- ISO 18553 originally is a method for rating pigmented spots, i.e. serves to determine how well pigments are dispersed in a polymer. As the dispersion of the pigment is dependent on the overall homogeneity of the polymer because inhomogeneities of the polymer are not coloured by the pigment, ISO 18553 can also be used as a measure for the homogeneity of a polymer by counting the non-coloured white spots and rating them according to the ISO 18553 scheme.
- the white spot area test As a further measure for the homogeneity of a polymer, the white spot area test has been developed which to a far extent is based on the modified ISO 18553 white spot rating test as described in the above paragraph. This test is described in detail below.
- homogeneity of a multimodal polymer composition can be improved by applying multiple compounding steps and/or particular compounding conditions to the resin coming from the reactor. These measures, however, have the disadvantage that they are associated with a significant increase in production costs for the composition.
- an object of the present invention to provide a multimodal polyethylene composition, comprising inter alia an ultrahigh molecular weight fraction, with improved homogeneity and thus improved properties, in particular surface properties.
- a multimodal polyethylene composition having improved homogeneity directly after its production.
- the composition should have good processing and good mechanical properties
- the present invention provides in a first embodiment a polyethylene composition
- a base resin comprising three ethylene homo- or copolymer fractions (A), (B) and (C) with different weight average molecular weight M w , wherein
- the present invention furthermore provides in a second a polyethylene composition
- a base resin comprising three ethylene homo- or copolymer fractions (A), (B) and (C) with different weight average molecular weight M w , wherein
- the polyethylene compositions according to the invention have an improved microscopic mixing directly after its production, which is demonstrated by the fact that already after a single, usual compounding step a resin with an excellent homogeneity is obtained.
- the composition combines good mechanical with good surface properties and hence e.g. an improved impact strength with an improved appearance of the final product.
- base resin means the entirety of polymeric components in the polyethylene composition according to the invention, usually making up at least 90 wt% of the total composition.
- the base resin in its entirety is consisting of fractions (A), (B) and (C).
- additives for utilization with polyolefins such as pigments (for example carbon black), stabilizers (antioxidant agents), antacids and/or anti-UVs, antistatic agents and utilization agents (such as processing aid agents) may be present in the polyethylene composition.
- pigments for example carbon black
- stabilizers antioxidant agents
- antacids and/or anti-UVs antistatic agents and utilization agents
- processing aid agents such as processing aid agents
- the amount of these additives is 10 wt% or below, further preferred 8 wt% or below, of the total composition.
- the composition comprises carbon black in an amount of 8 wt% or below, further preferred of 1 to 4 wt%, of the total composition.
- the amount of additives different from carbon black is 1 wt% or less, more preferably 0.5 wt% or less.
- a polyethylene composition comprising at least two polyethylene fractions, which have been produced under different polymerisation conditions resulting in different (weight average) molecular weights for the fractions, is referred to as "multimodal".
- multi relates to the number of different polymer fractions the composition is consisting of.
- the composition according to the present invention consists of the three fractions (A), (B) and (C) is it usually referred to as "trimodal".
- the form of the molecular weight distribution curve i.e. the appearance of the graph of the polymer weight fraction as function of its molecular weight, of such a multimodal polyethylene will show two or more maxima or at least be distinctly broadened in comparison with the curves for the individual fractions.
- a polymer is produced in a sequential multistage process, utilising reactors coupled in series and using different conditions in each reactor, the polymer fractions produced in the different reactors will each have their own molecular weight distribution and weight average molecular weight.
- the molecular weight distribution curve of such a polymer is recorded, the individual curves from these fractions are superimposed into the molecular weight distribution curve for the total resulting polymer product, usually yielding a curve with two or more distinct maxima.
- the composition preferably has a rating in the ISO 18553 white spot rating test of below 4.5.
- the base resin preferably has an MFR 5 of 0.1 g/10min or above, further preferred of 0.15 g/10min or above.
- the base resin preferably has an MFR 5 of 10 g/10min or below, more preferably 5 g/10min or below, and most preferably 2 g/10min or below.
- the base resin preferably has an MFR 21 of 1 to 50 g/10min.
- the FRR 21/5 of the base resin preferably is from 10 to 100, and more preferably is from 15 to 70.
- the density of the base resin is preferably 915 kg/m 3 or more, more preferably 930 kg/m 3 or more. Further, the density of the base resin is preferably 970 kg/m 3 or less.
- the weight average molecular weight of the base resin preferably is from 100,000 to 1,000,000 g/mol, and more preferably from 200,000 to 800,000 g/mol.
- the composition according to the invention measured after a single compounding step as defined below, has a white spot area of 0.01 to 1 %.
- the polyethylene composition after said single compounding step, has a white spot area of 0.7 % or below, usually of 0.01 to 0.7 %.
- the polyethylene composition measured after a single compounding step as defined below, preferably has a rating in the ISO 18553 white spot rating test of below 4, more preferred of below 3.
- the composition after said single compounding step, has a rating in the ISO 18553 white spot test of preferably 0.01 to below 4, more preferably of 0.01 to below 3.
- fraction (A) is present in the base resin in an amount of from 0.5 to 15 wt%, more preferred in an amount of from 0.5 to 10 wt% and still more preferred in an amount of from 0.5 to 5 wt%.
- Fraction (A) preferably has a density of 900 kg/m 3 or more, more preferably of 915 kg/m 3 or more. Further, fraction (A) preferably has a density of 980 kg/m 3 or less, more preferably of 965 kg/m 3 or less.
- Fraction (B) preferably is present in the base resin in an amount of 20 to 60 wt% of the base resin.
- fraction (B) preferably is an ethylene homopolymer.
- Fraction (B) preferably has a density of 915 kg/m 3 or more, more preferably of 940 kg/m 3 or more. Further, fraction (B) preferably has a density of 980 kg/m 3 or less.
- Fraction (C) preferably is present in the base resin in an amount of 20 to 60 wt% of the base resin.
- fraction (C) of the polyethylene composition is a copolymer of ethylene with one or more alpha-olefin comonomers.
- the alpha-olefin comonomer of fraction (C) is having from 4 to 8 carbon atoms, and more preferably is selected from 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.
- the polyethylene composition according to the invention preferably has a MFR 5 of 0.15 g/10min or above, more preferably 0.20 g/10min or above.
- the polyethylene composition according to the invention preferably has a shear thinning index SHI (2.7/210) of 5 to 300, more preferably of 10 to 280, still more preferably of 15 to 260, and most preferably of 17 to 150.
- SHI shear thinning index
- the SHI is the ratio of the viscosity of the polyethylene composition at different shear stresses.
- the shear stresses at 2.7 kPa and 210 kPa are used for calculating the SHI 2.7/210 which may serve as a measure of the broadness of the molecular weight distribution.
- the polyethylene composition preferably has a viscosity at a shear stress of 2.7 kPa (eta (2.7) ) of 10 to 500 kPas, more preferably 20 to 450 kPas and most preferably 40 to 400 kPas.
- the polyethylene composition according to the invention preferably has a value for eta 747 of 550 kPas or higher, more preferably of 600 kPas or higher.
- fractions (A), (B) and (C) of the composition of the present invention are given, these values are generally valid for the cases in which they can be directly measured on the respective fraction, e.g. when the fraction is separately produced or produced in the first stage of a multistage process.
- the base resin may also be and preferably is produced in a multistage process wherein e.g. fractions (A), (B) and (C) are produced in subsequent stages.
- the properties of the fractions produced in the second and third step (or further steps) of the multistage process can either be inferred from polymers, which are separately produced in a single stage by applying identical polymerisation conditions (e.g. identical temperature, partial pressures of the reactants/diluents, suspension medium, reaction time) with regard to the stage of the multistage process in which the fraction is produced, and by using a catalyst on which no previously produced polymer is present.
- the properties of the fractions produced in a higher stage of the multistage process may also be calculated, e.g. in accordance with B. Hagström, Conference on Polymer Processing (The Polymer Processing Society), Extended Abstracts and Final Programme, Gothenburg, August 19 to 21, 1997, 4:13.
- the properties of the fractions produced in higher stages of such a multistage process can be determined by applying either or both of the above methods.
- the skilled person will be able to select the appropriate method.
- Fraction (A) preferably has a weight average molecular weight of from 600,000 g/mol to 5,000,000 g/mol, more preferably from 600,000 to 2,000,000 g/mol.
- Fraction (A) preferably has an MFR 21 of 10 g/10min or below, more preferably of 5 or below.
- Fraction (B) preferably has a weight average molecular weight of from 2,000 g/mol to 50,000 g/mol, more preferably from 5,000 to 30,000 g/mol.
- Fraction (B) of the polyethylene composition preferably has an MFR 2 of 10 g/10 min or more, more preferably of 80 g/10min or more.
- the weight average molecular weight of fraction (C) is preferably from 30,000 to 600,000 g/mol, more preferably from 50,000 to 500,000 g/mol.
- Ziegler-Natta (ZN) or metallocene catalysts are preferably used, more preferably Ziegler-Natta catalysts.
- the catalyst may be supported, e.g. with conventional supports including silica, Al-containing supports and magnesium dichloride based supports.
- the catalyst is a ZN catalyst, more preferably the catalyst is non-silica supported ZN catalyst, and most preferably MgCl 2 -based ZN catalyst.
- the Ziegler-Natta catalyst further preferably comprises a group 4 (group numbering according to new IUPAC system) metal compound, preferably titanium, magnesium dichloride and aluminium.
- the catalyst may be commercially available or be produced in accordance or analogously to the literature.
- reference is made to WO2004055068 and WO2004055069 of Borealis and EP0 810 235.
- the content of these documents in its entirety is incorporated herein by reference, in particular concerning the general and all preferred embodiments of the catalysts described therein as well as the methods for the production of the catalysts.
- Particularly preferred Ziegler-Natta catalysts are described in EP 0 810 235.
- the base resin of the polyethylene composition according the invention preferably is produced so that at least one of fractions (B) and (C), preferably (C), is produced in a gas-phase reaction.
- one of the fractions (B) and (C) of the base resin, preferably fraction (B), is produced in a slurry reaction, preferably in a loop reactor.
- polyethylene base resin preferably is produced in a multistage process.
- Polymer compositions produced in such a process are also designated as "in-situ"-blends.
- a multistage process is defined to be a polymerisation process in which a polymer comprising two or more fractions is produced by producing each, or at least two, polymer fraction(s) in a separate reaction stage, usually with different reaction conditions in each stage, in the presence of the reaction product of the previous stage which comprises a polymerisation catalyst.
- fractions (A), (B) and (C) of the polyethylene composition are produced in different stages of a multistage process.
- the multistage process comprises at least one gas phase stage in which, preferably, fraction (C) is produced.
- fraction (C) is produced in a subsequent stage in the presence of fraction (B) which has been produced in a previous stage.
- the main polymerisation stages of the multistage process are such as described in EP 517 868, i.e. the production of fractions (B) and (C) is carried out as a combination of slurry polymerisation for fraction (B)/gas-phase polymerisation for fraction (C).
- the slurry polymerisation is preferably performed in a so-called loop reactor. Further preferred, the slurry polymerisation stage precedes the gas phase stage.
- the main polymerisation stages i.e. the production of fractions (B) and (C) are preceded by the production of fraction (A) in a first stage.
- Fraction (A) is preferably an ethylene homopolymer.
- this first polymerisation stage which may be designated as prepolymerisation, preferably all of the catalyst is charged into a loop reactor and the polymerisation is preferably performed as a slurry polymerisation.
- the resulting end product consists of an intimate mixture of the polymers from the different polymerisation stage.
- the different molecular-weight- distribution curves of these polymers together form a molecular-weight- distribution curve having a broad maximum or several maxima, i.e. the end product is a multimodal polymer mixture.
- the multimodal base resin of the polyethylene composition according to the invention is a trimodal polyethylene mixture consisting of fractions (B) and (C), and fraction (A). It is also preferred that this trimodal polymer mixture has been produced by polymerisation as described above under different polymerisation conditions in two or more polymerisation reactors connected in series. Owing to the flexibility with respect to reaction conditions thus obtained, it is most preferred that the polymerisation is carried out in a loop reactor/a gas-phase reactor combination.
- the polymerisation conditions in the preferred multistage method are so chosen that the comparatively low-molecular weight polymer (B), preferably having no content of comonomer, is produced in one stage, preferably the first stage after prepolymerisation of fraction (A), owing to a high content of chain-transfer agent (hydrogen gas), whereas the high-molecular weight polymer (C), preferably having a content of comonomer, is produced in another stage, preferably the second stage.
- This preferred order of stages may, however, be reversed.
- the temperature in the loop reactor where preferably fraction (B) is produced is preferably is 85 to 115 °C, preferably 90 to 105 °C and most preferably 92 to 98 °C.
- the temperature in the gas-phase reactor, where preferably fraction (C) is produced is 70 to 105 °C, more preferably is 75 to 100 °C, and most preferably is 82 to 97 °C.
- a chain-transfer agent preferably hydrogen, is added as required to the reactors, and preferably 100 to 800 moles of H 2 /kmoles of ethylene are added to the reactor, when the LMW fraction is produced in this reactor, and 0 to 50 moles of H 2 /kmoles of ethylene are added to the gas phase reactor when this reactor is producing the HMW fraction.
- the base resin of the polyethylene composition is produced with a rate of at least 5 tons/h, more preferably at least 10 ton/h, and most preferably at least 15 tons/h.
- composition of the invention preferably if produced in a process comprising compounding step, wherein the composition of the base resin, i.e. the blend, which is typically obtained as a base resin powder from the reactor, is extruded in an extruder and then pelletised to polymer pellets in a manner known in the art.
- the composition of the base resin i.e. the blend, which is typically obtained as a base resin powder from the reactor, is extruded in an extruder and then pelletised to polymer pellets in a manner known in the art.
- additives or other polymer components can be added to the composition during the compounding step in the amount as described above.
- the composition of the invention obtained from the reactor is compounded in the extruder together with additives in a manner known in the art.
- the extruder may be e.g. any conventionally used extruder.
- an extruder for the present compounding step may be those as supplied by Japan steel works, Kobe steel or Farrel-Pomini, e.g. JSW 460P.
- the extrusion step is carried out using production rates of at least 400, at least 500, at least 1000 kg/h may be used in said compounding step.
- the compounding step can be effected with production rate of that least 5 tons/h, preferably at least 15 tons/h, more preferably at least 20 or 25 tons/h or even at least 30 or more tons/h, such as at least 50, such 1-50, preferably 5-40, 10-50, in some embodiments 10-25 tons/h.
- production rates at least 20 tons/h, preferably at least 25 tons/h, even at least 30 tons/h, e.g. 25-40 tons/h may be desired during the compounding step.
- the present multimodal polyethylene composition of the invention enables such production rates within the property window of the invention, i.e. with various property combinations of MFR's of the fractions and of final base resin variations together with excellent homogeneity, just to mention few.
- a total SEI (specific energy input) of the extruder may be at least 150, 150-400, 200-350, 200-300 kWh/ton.
- the temperature of the polymer melt may vary in the extruder, the highest (max) melt temperature of the composition in the extruder during the extrusion step is typically more than 150°C, suitably between 200 to 350°C, preferably 250 to 310°C, more pref. 250 to 300°C.
- the benefit of the invention is that an excellent homogeneity can be obtained without extensive mixing, already by effecting once the compounding step, e.g. the preferable extrusion with production rates as defined above, and additionally, together with the high level homogeneity desirable polymer properties can be achieved/maintained.
- the present invention relates to an article, such as a pipe, an injection moulded article, a wire or cable, or a high density film, comprising a polyethylene composition as described above, and to the use of such a polyethylene composition for the production of such an article.
- a waters 150CV plus instrument was used with column 3 x HT&E styragel from Waters (divinylbenzene) and trichlorobenzene (TCB) as solvent at 140 °C.
- the column set was calibrated using universal calibration with narrow MWD PS standards (the Mark Howings constant K: 9.54*10 -5 and a: 0.725 for PS, and K: 3.92*10 -4 and a: 0.725 for PE).
- the ratio of M w and M n is a measure of the broadness of the distribution, since each is influenced by the opposite end of the "population".
- Density is measured according to ISO 1872, Annex A.
- the melt flow rate is determined according to ISO 1133 and is indicated in g/10 min.
- the MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer.
- the MFR is determined at 190°C and may be determined at different loadings such as 2.16 kg (ISO 1133 condition D - "MFR 2 "), 5 kg (ISO 1133 condition T - "MFR 5 ”) or 21.6 kg (ISO 1133 condition G - "MFR 21 ").
- FRR flow rate ratio
- Rheological parameters such as Shear Thinning Index SHI and Viscosity are determined by using a rheometer, preferably a Rheometrics Phisica MCR 300 Rheometer. The definition and measurement conditions are described in detail on page 8 line 29 to page 11, line 25 of WO 00/22040.
- the polymer composition according to the present invention has an improved homogeneity directly after its production in the polymerisation reactor.
- homogeneity is usually measured only on a compounded composition
- second, the way in which compounding is carried out has a decisive influence on the homogeneity of the compounded composition, it is important that the compounding conditions to which the composition is subjected and the compounding equipment used are/is clearly defined before homogeneity of the composition is determined, e.g. in terms of the white spot area test or the modified ISO 18553 white spot rating test as described below.
- compositions described herein are determined after a single compounding step only, which is to be carried out as follows:
- the base resin powder coming from the reactor is transferred, e.g. via intermediate holding tanks (50-250 tons), to the compounding unit without extra handling like grinding or cooling or similar processes.
- the powder is then poured into the inlet of the compounder together with the appropriate amounts of additives.
- the additives can be, typically, stearates, antioxidants, UV-stabilisers, or pigments/carbon blacks.
- the additives can be added as a pure component or as a master batch with a PE carrier.
- the base resin plus additives are then passed through the compounding unit only once.
- the idea of the single compounding step is that a reactor powder is allowed only one single pass through the compounding unit.
- the equipment to be used for the single compounding step is a twin-screw extruder like counter rotating equipment as supplied by Japan steel works, e.g. CIM JSW 460P or equivalent equipment.
- Typical compounding conditions in the single compounding step used in CIM JSW 460P having a screw diameter of 460 mm are: production: 25 to 30 tons/h mixer specific energy input (SEI): 260 kWh/ton gear pump SEI: 19 kWh/ton Temp. before gear pump: 290 °C Temp. after gear pump: 300 °C suction pressure gear pump: 1.6 bar mixer speed: 400 rpm
- the white spot area of the once compounded composition is determined at least partly following ISO 18553, as follows:
- a sample of a composition (including a pigment to make the inhomogeneities visible, e.g. carbon black in an amount of around 2.5 wt%) which is obtained after a single compounding step as described above, is analysed by first obtaining 6 microtome cuts of 6 different parts of the sample (thickness ⁇ 60 micrometer, diameter 3 to 5 mm).
- the cuts are evaluated at a magnification of 100, and the size, i.e. the part of the surface, of the non-coloured inclusions ("white spots", agglomerates, particles) on a total surface of each cut of 0.7 mm 2 is determined. All white spots with a diameter > 5 microns are counted. The "white spot area” is then expressed as the averaged fraction of the white spots on the total surface of the sample cut.
- homogeneity complementary is determined according to the modified ISO 18553 white spot rating test.
- inhomogeneities of the composition present after a single compounding step as described above, which appear as white spots are determined and rated according to the rating scheme given in ISO 18553. The lower the composition is rated in this test, the better is the homogeneity of the composition.
- Lynx 200 available from Engelhard Corporation Pasadena, U.S.A. has been used for Example 1.
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Claims (19)
- - Composition de polyéthylène comprenant une résine basique comprenant trois fractions d'homo- ou copolymère d'éthylène (A), (B) et (C) présentant différents poids moléculaires moyens Mw, oùa) la fraction (A) présente un MFR21 inférieur ou égal à 20 g/10 min,b) la fraction (B) présente un poids moléculaire moyen inférieur à celui de la fraction (C),c) la fraction (C) présente un poids moléculaire moyen inférieur à celui de la fraction (A),d) la composition présente une viscosité à une force de cisaillement de 747 Pa (eta747) supérieure ou égale à 350 kPas, ete) la composition présente un MFR5 supérieur ou égal à 0,15 g/10 min et une surface de points blancs de 1 % ou moins.
- - Composition de polyéthylène comprenant une résine basique comprenant trois fractions d'homo- ou copolymère d'éthylène (A), (B) et (C) présentant différents poids moléculaires moyens Mw, oùa) la fraction (A) présente un MFR21 inférieur ou égal à 20 g/1 0 min,b) la fraction (B) présente un poids moléculaire moyen inférieur à celui de la fraction (C),c) la fraction (C) présente un poids moléculaire moyen inférieur à celui de la fraction (A),d) la composition présente une eta747 supérieure ou égale à 350 kPas, ete) la composition présente un MFR5 supérieur ou égal à 0,15 g/10 min et un taux dans le test du taux de points blancs de la norme ISO 18553 inférieur à 4,5.
- - Composition de polyéthylène selon la revendication 1, où la composition présente un taux dans le test du taux de points blancs de la norme ISO 18553 inférieur à 4,5.
- - Composition de polyéthylène selon l'une quelconque des revendications précédentes, où la fraction (B) est présente dans la résine basique en une quantité de 20 à 60 % en poids de la résine basique.
- - Composition de polyéthylène selon l'une quelconque des revendications précédentes, où la fraction (C) est présente dans la résine basique en une quantité de 20 à 60 % en poids de la résine basique.
- - Composition de polyéthylène selon l'une quelconque des revendications précédentes, où la fraction (B) est un homopolymère d'éthylène.
- - Composition de polyéthylène selon l'une quelconque des revendications précédentes, où la fraction (C) est un copolymère d'éthylène avec un ou plusieurs co-monomères d'alpha-oléfine.
- - Composition de polyéthylène selon l'une quelconque des revendications précédentes, où la fraction (A) présente une densité de 900 à 980 kg/m3, de préférence de 915 à 965 kg/m3.
- - Composition de polyéthylène selon l'une quelconque des revendications précédentes, où la fraction (B) présente une densité de 915 à 980 kg/m3, de préférence de 940 à 980 kg/m3.
- - Composition de polyéthylène selon l'une quelconque des revendications précédentes, où la résine basique présente une densité de 915 à 970 kg/m3, de préférence de 930 à 970 kg/m3.
- - Composition de polyéthylène selon l'une quelconque des revendications précédentes, où la résine basique présente un MFR5 de 0,1 à 10 g/10 min.
- - Composition de polyéthylène selon l'une quelconque des revendications précédentes, où la résine basique a été produite avec une vitesse d'au moins 5 tonnes/heure.
- - Composition de polyéthylène selon l'une quelconque des revendications précédentes, où les fractions (A), (B) et (C) ont été produites à différentes étapes d'un procédé multi-étapes.
- - Procédé pour la production d'une composition de polyéthylène selon l'une quelconque des revendications précédentes, lequel procédé comprend la production des fractions (A), (B) et (C) en présence d'un catalyseur Ziegler-Natta.
- - Procédé selon la revendication 14, où les fractions (A), (B) et (C) sont produites à différentes étapes d'un procédé multi-étapes.
- - Article comprenant une composition de polyéthylène selon l'une quelconque des revendications 1 à 13.
- - Article selon la revendication 16, où l'article est un tuyau.
- - Utilisation d'une composition de polyéthylène selon l'une quelconque des revendications 1 à 13 pour la production d'un article.
- - Utilisation selon la revendication 18, dans laquelle l'article est un tuyau.
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
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ES04026094T ES2278263T3 (es) | 2004-11-03 | 2004-11-03 | Compuesto de polietileno multimodal con homogeneidad mejorada. |
AT04026094T ATE349489T1 (de) | 2004-11-03 | 2004-11-03 | Multimodale polyethylenzusammensetzung mit verbesserter homogenität |
DE602004003960T DE602004003960T2 (de) | 2004-11-03 | 2004-11-03 | Multimodale Polyethylenzusammensetzung mit verbesserter Homogenität |
PT04026094T PT1655334E (pt) | 2004-11-03 | 2004-11-03 | Composição de polietileno multimodal com homogeneidade melhorada |
EP04026094A EP1655334B1 (fr) | 2004-11-03 | 2004-11-03 | Composition de polyéthylène multimodal avec homogénéité améliorée |
CN2005800338765A CN101035851B (zh) | 2004-11-03 | 2005-11-02 | 具有改良的均一性的多峰聚乙烯组合物 |
KR1020077008763A KR100908391B1 (ko) | 2004-11-03 | 2005-11-02 | 균질성이 개선된 멀티모달 폴리에틸렌 조성물 |
AU2005300654A AU2005300654B2 (en) | 2004-11-03 | 2005-11-02 | Multimodal polyethylene composition with improved homogeneity |
EA200700732A EA011511B1 (ru) | 2004-11-03 | 2005-11-02 | Полиэтиленовая композиция (варианты), ее применение, способ ее получения и изделие, содержащее композицию |
PCT/EP2005/011721 WO2006048257A1 (fr) | 2004-11-03 | 2005-11-02 | Composition de polyethylene multimodale presentant une homogeneite amelioree |
US11/718,018 US20090252910A1 (en) | 2004-11-03 | 2005-11-02 | Multimodal polyethylene composition with improved homogeneity |
ARP050104614A AR051615A1 (es) | 2004-11-03 | 2005-11-03 | Composicion de polietileno multimodal con homogeneidad mejorada |
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EP04026094A EP1655334B1 (fr) | 2004-11-03 | 2004-11-03 | Composition de polyéthylène multimodal avec homogénéité améliorée |
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EP1655334A1 EP1655334A1 (fr) | 2006-05-10 |
EP1655334B1 true EP1655334B1 (fr) | 2006-12-27 |
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US (1) | US20090252910A1 (fr) |
EP (1) | EP1655334B1 (fr) |
KR (1) | KR100908391B1 (fr) |
CN (1) | CN101035851B (fr) |
AR (1) | AR051615A1 (fr) |
AT (1) | ATE349489T1 (fr) |
AU (1) | AU2005300654B2 (fr) |
DE (1) | DE602004003960T2 (fr) |
EA (1) | EA011511B1 (fr) |
ES (1) | ES2278263T3 (fr) |
PT (1) | PT1655334E (fr) |
WO (1) | WO2006048257A1 (fr) |
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FI111372B (fi) * | 1998-04-06 | 2003-07-15 | Borealis Polymers Oy | Olefiinien polymerointiin tarkoitettu katalyyttikomponentti, sen valmistus ja käyttö |
SE9803501D0 (sv) * | 1998-10-14 | 1998-10-14 | Borealis Polymers Oy | Polymer composition for pipes |
EP1041113A1 (fr) * | 1999-03-30 | 2000-10-04 | Fina Research S.A. | Polyolefines et leurs applications |
ATE316116T1 (de) * | 2000-04-13 | 2006-02-15 | Borealis Tech Oy | Polymerzusammensetzung für rohre |
US7192601B2 (en) * | 2002-01-18 | 2007-03-20 | Walker Edward B | Antimicrobial and sporicidal composition |
ES2268470T3 (es) * | 2002-12-24 | 2007-03-16 | Basell Polyolefine Gmbh | Composicion de polietileno para el moldeo por soplado destinadada a la produccion de grandes recipientes. |
EP1460105B1 (fr) * | 2003-03-20 | 2012-05-23 | Borealis Technology Oy | Composition de polymères |
-
2004
- 2004-11-03 AT AT04026094T patent/ATE349489T1/de not_active IP Right Cessation
- 2004-11-03 DE DE602004003960T patent/DE602004003960T2/de active Active
- 2004-11-03 EP EP04026094A patent/EP1655334B1/fr active Active
- 2004-11-03 ES ES04026094T patent/ES2278263T3/es active Active
- 2004-11-03 PT PT04026094T patent/PT1655334E/pt unknown
-
2005
- 2005-11-02 AU AU2005300654A patent/AU2005300654B2/en not_active Ceased
- 2005-11-02 CN CN2005800338765A patent/CN101035851B/zh active Active
- 2005-11-02 KR KR1020077008763A patent/KR100908391B1/ko active IP Right Grant
- 2005-11-02 WO PCT/EP2005/011721 patent/WO2006048257A1/fr active Application Filing
- 2005-11-02 EA EA200700732A patent/EA011511B1/ru not_active IP Right Cessation
- 2005-11-02 US US11/718,018 patent/US20090252910A1/en not_active Abandoned
- 2005-11-03 AR ARP050104614A patent/AR051615A1/es unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2720143C1 (ru) * | 2016-09-28 | 2020-04-24 | Бореалис Аг | Способ получения композиции мультимодального покрытия |
WO2018095772A2 (fr) | 2016-11-25 | 2018-05-31 | Borealis Ag | Nouvelle composition et procédé |
Also Published As
Publication number | Publication date |
---|---|
CN101035851B (zh) | 2010-11-24 |
EA200700732A1 (ru) | 2007-10-26 |
US20090252910A1 (en) | 2009-10-08 |
DE602004003960T2 (de) | 2007-11-08 |
KR20070065389A (ko) | 2007-06-22 |
AU2005300654A1 (en) | 2006-05-11 |
KR100908391B1 (ko) | 2009-07-20 |
CN101035851A (zh) | 2007-09-12 |
DE602004003960D1 (de) | 2007-02-08 |
AR051615A1 (es) | 2007-01-24 |
ATE349489T1 (de) | 2007-01-15 |
ES2278263T3 (es) | 2007-08-01 |
EA011511B1 (ru) | 2009-04-28 |
PT1655334E (pt) | 2007-03-30 |
WO2006048257A1 (fr) | 2006-05-11 |
AU2005300654B2 (en) | 2009-05-28 |
EP1655334A1 (fr) | 2006-05-10 |
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